200906713 九、發明說明： 【發明所屬之技術領域】 本發明係關於以所謂“卓氏”（C ζ 〇 c h r a 1 s k i)拉製技術循 環惰性氣體特別是氦的方法以及執行之的系統。 【先前技術】 在全世界能源背景下，光伏打電力市場目前正經歷前 所未有的成長。2004年由光伏打科技所生產的電力是126〇 MWp ’並且將會在20 1 〇年增加4倍而達到大約5 〇〇〇 M Wp。 產生將太陽能轉換成電力的太陽能板之製造程序包含 幾個技術步驟。主要的步驟用單晶或多晶矽作為活性轉換 材料’根據以下的程序： 多晶石夕顆粒的製造； 鑄錠的製造； 基板的裁切；200906713 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method of circulating an inert gas, particularly helium, in a technique known as "C r 〇 c h r a 1 s k i", and a system for performing the same. [Prior Art] In the global energy background, the photovoltaic power market is currently experiencing unprecedented growth. The electricity produced by Photovoltaic Technology in 2004 was 126 〇 MWp ′ and will increase four times in the 21 〇 year to reach approximately 5 〇〇〇 M Wp. The manufacturing process for generating solar panels that convert solar energy into electricity involves several technical steps. The main steps are to use single crystal or polycrystalline germanium as the active conversion material' according to the following procedure: fabrication of polycrystalline granules; manufacture of ingots; cutting of substrates;
晶格的製造；與 嵌板的製造 單晶^格具有允許製造高效率太陽能模組的優勢， 但疋其成本比由多晶矽所製成的高。 在2004年，結晶石夕的總市場佔 晶矽伯了 32%。在201()年， 中单 早日日矽市場將在將成為 四七大的總市場裡所產出的電力只佔有。 卓氏拉製技術（以下稱為CZ技淋、少妖、仕 石夕，然後該經純化的矽被用來加帛經純化的 器。將該力，放置在加熱石墨掛:=被:至生長反應 r ;化。從晶種開始， 6 200906713 在非常精確的操作條件下執行鑄㈣ 別是掛堝的溫度、炫融加料的溫度、外：轉拉出，特 度、熱轉移與晶種 μ的溫度、溫度梯 «促w租出逮率。此择 s 常是氬）下執行，兮钟伴^ m 奋作疋在純惰性氛圍（通 錢惰性氛圍通常連續地 構成惰性氛圍的汙举洛挪；必λ 牡表私中庄入。 左1 體被移除（排出氣體）。在拉製μ 情性氣體流主要會受到㈣、。〇、。〇2及〇 =… 可能被空氣和溼氣二次污染。 2的汙木。亦有Fabrication of Lattices; and Fabrication of Panels Single crystals have the advantage of allowing the fabrication of high efficiency solar modules, but at a higher cost than those made of polysilicon. In 2004, the total market for Crystal Shi Xi was 32%. In the 201() year, the market will only occupy the electricity generated in the total market that will become the May 7th. Zhuo's drawing technology (hereinafter referred to as CZ technology shower, Shao Yao, Shi Shi Xi, then the purified crucible is used to add the purified device. The force is placed on the heated graphite hanging: = is: to Growth reaction r; crystallization. Starting from seed crystal, 6 200906713 Execution of casting under very precise operating conditions (4) Temperature of hang-up, temperature of smelting feed, external: transfer, speciality, heat transfer and seed crystal The temperature and temperature of the μ are promoted. The choice is usually performed under argon. The 兮 伴 伴 m m 疋 疋 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在 在Lohne; must be λ, the watch is privately inserted. The left body is removed (exhaust gas). In the drawing of the modal gas flow will mainly be affected by (four), 〇, 〇 2 and 〇 = ... may be air and wet Secondary pollution of gas. 2 stained wood. Also have
在冷卻階段，惰性翕妒A 但是比較少的程度 …到同樣的汗染物所污染， 率。如此所得到的為不同直徑的鑄銳，其係取決於拉出速 前分配如下 攸夕矽晶粒製造太陽能板的產生成本目 38/〇用於矽鑄錠的製造與基板的裁切； 3〇%用於晶格製造；和 32%用於嵌板製造。 功的關鐽點之—，而 例如基板裁切的薄 成本的減少是光伏打技術未來成 目前正在測試每個步驟的解決方法 化0 至於由Cz技術製造鑄錠’以氦或以氦為主的混合物 與普遍：為製程氣體的氬置換’可提供生產力實質：增 加，其歸功於氦的較好熱性質。 使用虱作為製裎氣體有許多的參考文獻。例如GB-A-5 94 743描述使用諸如氦的惰性氣體來冷卻。 更^年來’ JP-A-9〇48695描述使用氦/氬混合物以減少 200906713 晶體裡氧的濃度。 曰二S:5 676 75〗敘述使用氦/氬混合物來更快速地冷卻 日曰體低於約攝氏600度0 沒有：人了解到’由於氣相較於氯成本較高，在 二m哀氦的製程的情況下，以純氦或以氛為 &物（例如氦/氬混合物哎 ’’’’ ' 經濟上並木叮> 次乳或任何其他惰性氣體）取代氬在 ，可订’因此期望能有循環氦的製程，可能以與 具他乳體之混合物循環。 〃 【發明内容】 :就是本發明係關於循環氨或以氨為主的混合物的方 法和糸統的理由，使得回收 .七化所有或大部分用在一舻 拉I與冷卻矽單晶且更特別的 ^ φ . ^ ^圖用在光伏打市場的矽 町衣％中的氦成為可能，其 低。 丹耵夕材枓的效能的要求係較 這就是本發明的標的為使用 的方半沾搜i甘姑 卓氏（Cz)技術製造矽鑄錠 的方法的理由，其特徵在於在 ^ ^ ^ ^ 马皁氏反應器的反應器或 疋稱為卓氏爐的爐裡用作惰性氣體之氦或 混合物在離開該卓氏反應器或該卓氏姨時乳體 連續步驟的處理： &盧時，係經包括以下 -步驟*冷卻射出氣體或射出氣體昆合物. -步驟b):壓縮在步驟a) 體混合物； 7部的射出氣體或射出氣 -步驟c):過濾在步驟b)巾 氣體混合物以從中去除固體粒；·、’的射出氣體或射出 /卞；與 200906713In the cooling phase, inert 翕妒A, but to a lesser extent...to the same sweat stains, the rate. The thus obtained castings of different diameters are distributed according to the distribution rate of the solar panels before the drawing speed is as follows. 38/〇 is used for the manufacture of the ingot casting and the cutting of the substrate; 〇% is used for lattice fabrication; and 32% is used for panel manufacturing. The key point of the work - and the thin cost reduction of, for example, the cutting of the substrate is the solution for the future of each step of the photovoltaic technology. As for the manufacture of ingots by Cz technology, The mixture and the general: argon replacement for process gases can provide substantial productivity: increased, thanks to the better thermal properties of the ruthenium. There are many references to the use of helium as a helium gas. For example, GB-A-5 94 743 describes the use of an inert gas such as helium for cooling. More than a year' JP-A-9〇48695 describes the use of a helium/argon mixture to reduce the concentration of oxygen in the crystal of 200906713.曰二S:5 676 75 〗 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述 叙述In the case of a process, the argon is replaced by a pure enthalpy or an atmosphere (for example, a argon/argon mixture 哎 ''' 'economically 叮 叮 次 次 或 或 or any other inert gas), so it is expected A process that can have a cyclical enthalpy may circulate with a mixture of his body. 〃 [Summary of the Invention]: The present invention relates to a method and a system of circulating ammonia or an ammonia-based mixture, so that recycling or all of the seven is used in a single pull I and a cooled single crystal and more The special ^ φ . ^ ^ figure is used in the photovoltaic market, the 氦 衣 % 氦 氦 氦 氦 氦 氦 氦 氦 氦 氦 氦 氦 氦. The requirement of the efficacy of Tanjong 枓 枓 is the reason why the method of the present invention is the method for manufacturing bismuth ingots by the use of the semi-consistency of the syllabus, which is characterized by ^ ^ ^ ^ The reactor of the horse soap reactor or the sputum of the furnace known as the Zhuo furnace is used as a mixture of inert gas or a mixture of the emulsion in the continuous step of leaving the Zhuo reactor or the Zhuo's reactor: & , comprising the following - step * cooling the injected gas or the injected gas compound. - Step b): compressing the body mixture in step a); ejecting gas or injecting gas in step 7 - step c): filtering in step b) a gas mixture to remove solid particles therefrom; ·, 'ejected gas or injection/卞; and 200906713
-1 X d):純化在步驟C)所過濾的射出氣體或射 體混合物以從中移除不純物。 ” 本方去所採用如上所定義的“以氦為主的氣體混合 一詞指稱么士 有5 〇體積％以上’較佳7 0體積％以上，最尤 /、疋95體積％以上的量的氦的氣體混合物。該混合物的其 ’成氣體特別從氧、氬與氮本身或其混合物中挑選。 "如上所疋義的方法中，離開該卓氏反應器或該卓氏爐 的氦或乂氦為主的氣體混合物-般於拉製階段主要受到氧 化石夕（SiO)、—氧化碟（⑶）、二氧化碳（。〇2)和有時候漫或 乾空氣的汙染。 冷部離開该卓氏反應器或該卓氏爐的氮或以氣為主的 氣體混合物之步驟a)係執行直到達到攝氏1〇〇度或更低的 溫度，更尤其是要遠到^ > f逆剞"於攝氏2〇度到25度之間的周圍 溫度。這導致氣態的氧化欲沾m i 乳化夕的固化，其固化溫度大約為攝 氏1100度，及其隨後之氧化矽回收。-1 X d): Purify the injected gas or mixture of shots filtered in step C) to remove impurities therefrom. The term "gas mixture based on yttrium as defined above is used to mean that the sputum has a volume of more than 5% by volume, preferably more than 70% by volume, most preferably, more than 95% by volume." A mixture of gases. The gas of the mixture is selected in particular from oxygen, argon and nitrogen itself or a mixture thereof. " In the above-mentioned method, the gas mixture which is the main gas or the ruthenium which leaves the Zhuo's reactor or the Zhuo's furnace is mainly subjected to the oxidized stone (SiO), the oxidation disk ( (3)), carbon dioxide (.〇2) and sometimes diffuse or dry air pollution. The step a) of the cold portion leaving the Zhuo's reactor or the gas or gas-based gas mixture of the Zhuo's furnace is performed until a temperature of 1 degree Celsius or lower is reached, more particularly to be far as ^ > f recursive " ambient temperature between 2 degrees Celsius and 25 degrees Celsius. This results in the solidification of the gaseous oxidizing agent, which cures at a temperature of about 1100 degrees Celsius and its subsequent cerium oxide recovery.
V 壓縮來自如上所定蠢的士 心我的方法之步驟勾所冷卻的氦或以 氦為主的氣體混合物之步驟k、t 驟b)使得達到隨後過濾與純化步V-compression steps from step sk, step b) of the 氦 or 氦-based gas mixture cooled by the steps of my method as described above, so that subsequent filtration and purification steps are achieved.
驟所需要的壓力成為可能。 A ~般而言，此壓力等於或大於 2 X 105帕’但不超過3〇xl〇5帕。 過濾來自步驟）3)所A— 7部的乱或以氦為主的氣體混合物 之步驟C )允δ午來自C z法的私7丄 *的板子被移除。 這個步驟由例如機插讲、、各上、， β ’慮或靜電過濾所組成。 純化來自如上所定Μ 我的方法之步驟C)之經冷卻的氦或 以氦為主的氣體混合物之牛_ v -V d)採用傳統氣體純化技術， 9 200906713 像是吸附於沸石，穿透 、”bh $透聚合物膜，催化氧化和低溫分離。 这二方法可結合或另外一 是活性碳的處理。 …的别純化步驟’像 【實施方式】 在執行本發明的較佳侔 人版入*, 1怿件下氣或以氦為主的氣體混 S物含有少於10PPm的殘餘不純物。 根據如同如上所定義#方法之一 ,-1 \ λΑ >- _L· 守寻殊方面’來自步 驟d)的氣或以氦為主的氣體混合物經 , 刀析，如果不純物的 各里超過預先決定的最大含 d)。 丹、、工又進一步的純化步驟 根據如上所定義的方法之另一 來白牛驟寺殊方面，包括儲存 後再㈣”氦為主的氣體混合物的步驟㈣別是隨 器或卓氏爐中作為惰性氣體者。尤其’ 田根據本發明的處理是意圖用在整 幾個卓氏爐的時候是报有用的。…卓氏反應益或 根據如上所定義的方法 氦$ k & 一個變體，來自步驟d)的 虱或以虱為主的軋體混合物再 氏爐中之惰性氣體。 用作為於該反應器或該卓 …至於再使S SI或以乳為主的氣體昆合物，如 5舌或如果必要的話，可加入氕和“、 果心要的 合物以補償由於循環和純化的損失或。#或多種其他氣體混 有利地，本發明的方法筏 去係連續地執行。 本發明的標的亦為執行該方 變體，其包含在惰性氛圍下兹丄系統和其如所定義的 心#氏拉製技#製造鑄鍵的 10 200906713 傳統裝置（n，κι Μ .X , 用於被汙乐的惰性氣體流或被 體混合物之迴路⑺，其與傳統裝置⑴的的惰性氣 裝置⑴的入口 t 允衣置⑴的出口連接且位在該 置（3)，至少伽厂 也至夕—個冷卻裝 -個純化裝置⑹。 ㈣濾裝置(5)與至少 # J套藉由CZ技術製造鑄錠的機器，有可能採用 幾個用來回此姐山产… 』此刼用 收排出氧體的裝置、返回迴路等等。 在執行本發明的較佳條件下， 法的系絲另认—a 用果貫订如上之處理方 装置之間包S-個緩衝槽⑺其安裝在過遽裝置和純化 洗除I:部:二系：尚包括用來分析排出氣流，其經 次邛刀可忐巧染物的裝置（8)。 在執行本發明的其他較佳 少 一個用來再彳丨^^ + 、 α上的系統尚包括 (25) . Α |Τ ^ 出虱^進入迴路的回流管線 ()其正好在壓縮機之前 ^ 所指出的所欲含量 4。如果不純物超過如上 了以使用此回流管線。 在執仃本發明的其他較佳條 — 女裝在如上之迴路上、介 Ik衝槽（7 ) 較佳而言，使❹執行Cz方裝置與傳統CZ裝置之間。 氣體是由該緩衝槽所供應的。法期間的全部或部份的惰性 為了要補乜在方法執行時 新鮮惰性氣體或氣體混合物的娃’提供一個用來儲存 戶斤田&卜主ω· ^ 、 存裝置（9)也是有利的。 所用的惰性氣體較佳包 "吧疋㈣的 根據本發明的處理 /、較佳由氦所組成。 '、、σ方法擁有非常有利的品質。 200906713 一個藉由Cz技術生產鑄錠的生產單元通常勺― 個拉製機。本發明特別地使循環整個生產單元或2 3幾十 的惰性氣體流的氦，或使每個拉製機具有—5套機器 為可能。第一個解決辦法意謂著只有單一的循枣 凡成 而使保養更容易但是需要在機器組的批次=裒置，從 當根據本發明替每個拉製機安裝循環單元，操/係作。 單，但是由於Cz機的數量增加因此需要更繁重:::更簡 執行如上之已描述過的方法的較錢件也適用二 如上之處理方法的系統。 ；執仃 參照如圖1的附圖將更清楚地了解本發明， _ :由、cz &生產鑄錠的單—站及其相關的氦或以氦為主員= 氣體混合物處理系統，其包含幾個 〃、、 裝置。 所耗及的可選擇的 ，傳統的CZ機顯示在圖的左邊。從緩衝槽供給—種或 夕種，性氣體。汙染的惰性氣體經過—個包含冷卻裝置， 允許氧化⑪以粉末的形式回收的迴路。 * ^ 丨术s踝將經如此 :二：帶進壓縮機。這條管線接有支線，支線的用途 緩衝神。壓縮的氣體然後導入過遽裳置，然後通入 ^ 示共他水物的純化裝置。麸 後經純化的氣體係經分析， ’、、、 ,,. 右具捋口 °又疋的標準，則允許 左、4化的軋體運送進入將使 衝槽。 1，、恧lz機惰性氛圍的緩 如果分析無法符合設定的桿準 ..,,,_ ^ ^ ^則支線會帶氣體流至 匕/慮的上％之一點，在目前 引例子會在壓縮機之前，但視所 12 200906713 使用的過濾技術而定，其可 次的處理。 能在壓縮機之後，以接受第二 由於損^ a , , , …、了避免的’故有新鮮氣體的獨立儲存， 如目刚的例子， ^乳體可能排放進入緩衝槽或可能被直接 傳迗’且與來自 ㈢緩衝槽的進料流平行，進入Cz機。 如同所述，士n卜夕、„ t 如上之迴路可能跟單一的Cz機或一組之 兩個或更多的Cz機使用。 【圖式簡單說明】 圖1，執行該方法的系統 【主要元件符號說明】 (1) 傳統裝置 (2) 迴路 (2')回流管線 (3) 冷卻骏置 (4) 壓縮機The pressure required for the trial is made possible. A ~ Generally, this pressure is equal to or greater than 2 X 105 Pascals' but not more than 3 〇 xl 〇 5 Pa. The step of filtering the chaotic or cesium-based gas mixture from step A) to step 3) is to remove the plate from the Cz method. This step consists of, for example, a machine plug-in, a top, a beta or an electrostatic filter. Purification of the calcined 氦 or v-based gas mixture from step C) of my method as defined above. _ v -V d) using conventional gas purification techniques, 9 200906713 is like adsorption to zeolite, penetration, "bh $ polymer permeable membrane, catalytic oxidation and low temperature separation. These two methods can be combined or the other is the treatment of activated carbon. [Other purification steps" like [Embodiment] In the implementation of the preferred human version of the present invention *, 1 下 gas or 氦-based gas mixture S contains less than 10 ppm of residual impurities. According to one of the methods defined as above, -1 \ λΑ >- _L· The gas of step d) or the gas mixture based on hydrazine is subjected to knife-cutting, if each of the impurities exceeds a predetermined maximum content of d). Further purification steps of Dan, according to the method as defined above In the case of Bai Niu Ju Temple, including the step of storing (4) the main gas mixture after storage (4), it is the inert gas in the follower or Zhuo's furnace. In particular, the treatment according to the present invention is intended to be useful in the case of several Zhuo's furnaces. ...Zhuo's reaction benefit or according to the method as defined above 氦$ k & a variant, the inert gas from the crucible of step d) or the crucible-based rolling mill mixture. Used as a reactor in the reactor or as a result of re-suppressing S SI or a milk-based gas compound, such as 5 tongues or, if necessary, adding hydrazine and ", a desired compound to compensate for the circulation Advantageously, the method of the present invention is carried out continuously in combination with a loss of purification or a plurality of other gases. The subject matter of the present invention is also to carry out the variant of the invention, which comprises a system of inert gas and its like The defined heart #氏拉制技术# manufacture of cast key 10 200906713 conventional device (n, κι Μ .X, for the inert gas flow or the mixture of the body mixture (7), which is compatible with the conventional device (1) The inlet t of the inert gas device (1) is connected to the outlet of the garment (1) and is located at the set (3), at least the plant is also cooled to a purification device (6). (4) The filter device (5) and at least #J sets In the case of a machine for manufacturing ingots by CZ technology, it is possible to use several devices for returning to this sister mountain... "This device uses a device for collecting oxygen, a return circuit, etc. Under the preferred conditions for carrying out the invention, The wire is different - a use between the above treatment devices S-buffer tank (7) is installed in the flooding device and the purification washing I: part: the second system: still includes a device (8) for analyzing the exhaust gas flow, which can be dyed by the secondary file. The other preferred ones are used to re-compute ^^ + , α on the system still includes (25) . Α |Τ ^ exit 进入 ^ into the return line of the loop () just before the compressor ^ pointed out Want to content 4. If the impurities exceed the above to use this reflux line. In the other preferred strip of the invention - the women's circuit on the above circuit, the Ik groove (7), preferably, the implementation of Cz Between the square device and the conventional CZ device. The gas is supplied by the buffer tank. All or part of the inertness during the process is provided for the purpose of storing a fresh inert gas or gas mixture during the execution of the method. It is also advantageous to use the yoghurt & ω·^, storage device (9). The inert gas used is preferably a package according to the invention, preferably consisting of 氦. The σ method has a very favorable quality. 200906713 A Cz technology The production unit for producing ingots is usually a scooping machine. The invention in particular makes it possible to circulate the entire production unit or a stream of 23 or more inert gas streams, or to have -5 sets of machines per drawing machine. The first solution means that only a single jujube is made to make maintenance easier but requires a batch in the machine group = from the installation of the cycle unit for each drawing machine according to the invention, Single, but because of the increase in the number of Cz machines, it needs to be more cumbersome::: The more simplified parts that implement the method described above are also applicable to the system of the above processing method. The invention will be more clearly understood from the drawings, _: a single station for the production of ingots from cz & and its associated crucible or crucible as a mains = gas mixture treatment system comprising several crucibles, devices. The optional, conventional CZ machine that is consumed is shown on the left side of the figure. From the buffer tank, a species or a species of sexual gas is supplied. The contaminated inert gas passes through a circuit containing a cooling device that allows the oxidation 11 to be recovered in the form of a powder. * ^ 丨 踝 踝 will be like this : Second: Bring into the compressor. This line is connected to a branch line, and the purpose of the branch line is to cushion the god. The compressed gas is then introduced into the sputum and then passed through a purification unit showing the water. After the bran, the purified gas system was analyzed, and the right 捋 ° ° ° 疋 标准 右 右 右 右 右 右 右 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 1, the 惰性lz machine inert atmosphere is slow if the analysis can not meet the set rod standard..,,, _ ^ ^ ^ then the branch line will bring the gas flow to one of the upper points of the 匕 / worry, in the current example will be compressed Before the machine, but depending on the filtering technology used by the 12 200906713, it can be processed second. Can be after the compressor to accept the second due to damage, a, and so on, so there is a separate storage of fresh gas, such as the example of the original, ^ milk may be discharged into the buffer tank or may be directly transmitted迗' and parallel to the feed stream from the (c) buffer tank, enter the Cz machine. As mentioned, the circuit above may be used with a single Cz machine or a group of two or more Cz machines. [Simplified Schematic] Figure 1. System for performing this method [mainly Description of component symbols] (1) Conventional device (2) Circuit (2') return line (3) Cooling stage (4) Compressor
(5) 過濾裝置 (6) 純化裴置 (7) 緩衝槽 (7，） 緩衝槽 (8) 裝置 (9) 儲存裝置 13(5) Filtration unit (6) Purification unit (7) Buffer tank (7,) Buffer tank (8) Unit (9) Storage unit 13